Pattern forming process and shrink agent

ABSTRACT

A negative pattern is formed by applying a resist composition onto a substrate, exposing the resist film, and developing the exposed resist film in an organic solvent developer. The process further involves coating the negative pattern with a shrink agent solution of a polymer comprising recurring units capable of forming lactam under the action of acid in a C 7 -C 16  ester or C 7 -C 16  ketone solvent, baking the coating, and removing the excessive shrink agent via organic solvent development for thereby shrinking the size of spaces in the pattern.

CROSS-REFERENCE TO RELATED APPLICATION

This non-provisional application claims priority under 35 U.S.C. §119(a) on Patent Application No. 2014-223972 filed in Japan on Nov. 4, 2014, the entire contents of which are hereby incorporated by reference.

TECHNICAL FIELD

This invention relates to a shrink agent and a pattern forming process comprising forming a resist pattern via resist coating, exposure and development, coating the resist pattern with a shrink agent, baking, and developing the shrink agent for shrinking the size of spaces in the resist pattern.

BACKGROUND ART

While the effort to reduce the pattern rule is in rapid progress to meet the recent demand for higher integration level and operating speed of LSIs, the photolithography is on widespread use. The photolithography has the essential limit of resolution determined by the wavelength of a light source. One micropatterning approach to go beyond the limit of resolution is by combining ArF excimer laser immersion lithography with double patterning. One typical version of double patterning is litho-etch-litho-etch (LELE) process involving forming a pattern via exposure, transferring the pattern to a hard mask on a substrate by etching, effecting second exposure at a half-pitch shifted position, and etching the hard mask. This process has the problem of misalignment between two exposures or overlay error. Another version of double patterning is self-aligned double patterning (SADP) process involving the steps of transferring a resist pattern to a hard mask, growing a film on opposite sides of hard mask features, and leaving sidewalls of film for thereby doubling pattern size. The SADP process needs exposure only once and mitigates the problem of overlay error. To simplify the process, a modified version of the SADP process of forming a silicon oxide film on sidewalls of resist pattern features as developed rather than sidewalls of hard mask features for thereby doubling pattern size is also proposed. Since the SADP process is successful in reducing the pitch of line pattern to half, the pitch can be reduced to ¼ by repeating the SADP process twice.

Not only shrinking of line patterns, but also shrinking of hole patterns is necessary. Unless the hole pattern is shrunk, shrinkage over the entire chip is incomplete. One known method of shrinking a hole pattern is RELACS® method described in JP-A H10-073927. This method intends to reduce the size of a hole pattern by coating a resist pattern as developed with a water-soluble material containing a crosslinker, and baking the coating to form a crosslinked layer on the resist surface for causing the resist pattern to be thickened. JP-A 2008-275995 describes a water-soluble shrink material comprising an amino-containing polymer or polyamine, which bonds to the resist surface via neutralization reaction with carboxyl groups on the resist surface, for thereby thickening the resist film. It is also proposed in Proc. SPIE Vol. 8323 p83230W-1 (2012) to shrink a hole pattern by utilizing the direct self-assembly (DSA) of a block copolymer.

Shrinkage by the RELACS® method has the problem that since a crosslinker becomes active with an acid catalyst within resist, the size of holes is non-uniform after shrinkage if acid diffusion is non-uniform. In the shrink method based on neutralization and bonding of water-soluble amino polymer, the pattern is thickened as direct reflection of irregularities on the resist surface so that dimensional variations of the resist pattern as developed and dimensional variations after shrinkage are identical. The shrink method utilizing the DSA function of a block copolymer has advantages including an increased amount of shrinkage and a minimal dimensional variation after shrinkage, but some problems. Namely, if the DSA is applied to holes of different size, shrinkage cannot be induced for those holes of the size that causes a contradictory assembly of block copolymer. If the DSA is applied to a trench pattern, shape deformation becomes a problem, for example, a plurality of hole patterns are formed.

There is a need for a shrink agent which can shrink a trench pattern without changing the shape of the resist pattern, and improve the dimensional variation and edge roughness (LWR) of the resist pattern after development.

CITATION LIST

-   Patent Document 1: JP-A H10-073927 (U.S. Pat. No. 6,579,657) -   Patent Document 2: JP-A 2008-275995 (US 20100119717) -   Non-Patent Document 1: Proc. SPIE Vol. 8323 p83230W-1 (2012)

SUMMARY OF INVENTION

As discussed above, the method of applying a RELACS® material of crosslink type or neutralizing reaction-mediated bond type onto a resist pattern causes no pattern deformation, but fails to reduce the dimensional variation of the resist pattern. The DSA method can reduce the dimensional variation of a hole pattern as developed, but invites pattern deformation when applied to a trench pattern as developed.

An object of the invention is to provide a shrink agent which when coated onto a resist pattern as developed, can reduce the dimensional variation of the resist pattern, and when applied to a trench pattern, can shrink the trench size without causing pattern deformation; and a pattern forming process using the same.

In one aspect, the invention provides a pattern forming process comprising the steps of applying a resist composition comprising a polymer comprising recurring units having an acid labile group-substituted carboxyl group, an acid generator and an organic solvent, onto a substrate, prebaking to form a resist film; exposing the resist film to high-energy radiation, baking the film; developing the exposed resist film in an organic solvent-based developer to form a negative resist pattern; applying a shrink agent onto the negative resist pattern, baking; and removing the excessive shrink agent with the organic solvent-based developer for thereby shrinking the size of spaces in the pattern. The shrink agent used herein is a solution of a polymer comprising recurring units (a1) having the general formula (1) in a solvent selected from the group consisting of ester solvents of 7 to 16 carbon atoms and ketone solvents of 7 to 16 carbon atoms.

Herein R¹ is hydrogen or methyl; R² is a straight or branched C₂-C₈ alkylene group; R³ is a straight, branched or cyclic C₁-C₈ alkyl group which may contain an ether moiety, ester moiety or halogen, or an acid labile group; X¹ is phenylene or —C(═O)—O—R⁴—; R⁴ is a single bond, a straight, branched or cyclic C₁-C₈ alkylene group, or phenylene group.

In a preferred embodiment, the polymer comprising recurring units (a1) in the shrink agent further comprises recurring units (b) having a hydroxyl, carboxyl, lactone ring, lactam ring, sultone ring, sulfone, sulfonic acid ester, sulfonamide, carboxylic acid amide, nitro, cyano, thienyl, furyl, pyrrole, acid anhydride, imide, —NH—(C═O)—O—, —S—(C═O)—O—, or —ON(═O₂)—.

In a preferred embodiment, the solvent in the shrink agent is at least one solvent selected from the group consisting of ester solvents of 7 to 16 carbon atoms including amyl acetate, isoamyl acetate, 2-methylbutyl acetate, hexyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, hexyl formate, ethyl valerate, propyl valerate, isopropyl valerate, butyl valerate, isobutyl valerate, tert-butyl valerate, amyl valerate, isoamyl valerate, ethyl isovalerate, propyl isovalerate, isopropyl isovalerate, butyl isovalerate, isobutyl isovalerate, tert-butyl isovalerate, isoamyl isovalerate, ethyl 2-methylvalerate, butyl 2-methylvalerate, ethyl pivalate, propyl pivalate, isopropyl pivalate, butyl pivalate, tert-butyl pivalate, ethyl pentenoate, propyl pentenoate, isopropyl pentenoate, butyl pentenoate, tert-butyl pentenoate, propyl crotonate, isopropyl crotonate, butyl crotonate, tert-butyl crotonate, butyl propionate, isobutyl propionate, tert-butyl propionate, benzyl propionate, ethyl hexanoate, allyl hexanoate, propyl butyrate, butyl butyrate, isobutyl butyrate, 3-methylbutyl butyrate, tert-butyl butyrate, ethyl 2-methylbutyrate, isopropyl 2-methylbutyrate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, ethyl phenylacetate, and 2-phenylethyl acetate, and ketone solvents of 7 to 16 carbon atoms including 2-heptanone, 3-heptanone, 4-heptanone, 2-octanone, 3-octanone, 4-octanone, 2-nonanone, 3-nonanone, 4-nonanone, 5-nonanone, diisobutyl ketone, ethylcyclohexanone, ethylacetophenone, ethyl n-butyl ketone, di-n-butyl ketone, and diisobutyl ketone.

In a preferred embodiment, the polymer in the resist composition comprises recurring units (a2) having the general formula (2).

Herein R⁵ is hydrogen or methyl, R⁶ is an acid labile group, Z is a single bond or —C(═O)—O—R⁷—, R⁷ is a straight, branched or cyclic C₁-C₁₀ alkylene group which may contain ether or ester, or naphthylene group, and 0<a2<1.0.

In a preferred embodiment, the developer comprises at least one organic solvent selected from the group consisting of 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone, methylcyclohexanone, acetophenone, methylacetophenone, propyl acetate, butyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate, butenyl acetate, propyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl valerate, methyl pentenoate, methyl crotonate, ethyl crotonate, methyl propionate, ethyl propionate, ethyl 3-ethoxypropionate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, amyl lactate, isoamyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, benzyl propionate, ethyl phenylacetate, and 2-phenylethyl acetate.

Typically, the high-energy radiation in the exposure step is i-line of wavelength 364 nm, KrF excimer laser of wavelength 248 nm, ArF excimer laser of wavelength 193 nm, EUV of wavelength 13.5 nm, or EB.

In another aspect, the invention provides a shrink agent comprising a polymer comprising recurring units (a1) having the general formula (1), defined above, and at least one solvent selected from ester solvents of 7 to 16 carbon atoms and ketone solvents of 7 to 16 carbon atoms.

The shrink agent may further comprise at least one of salt compounds having the general formulae (3)-1 and (3)-2: R⁸—CO₂ ⁻M⁺  (3)-1 R⁹—SO₃ ⁻M⁺  (3)-2 wherein R⁸ and R⁹ each are a straight, branched or cyclic C₁-C₂₀ alkyl group, C₂-C₂₀ alkenyl group or C₆-C₂₀ aryl group which may contain fluorine, ether, ester, lactone ring, lactam ring, carbonyl, amino or hydroxyl, and M is sulfonium, iodonium or ammonium.

Advantageous Effects of Invention

The process of the invention involves forming a resist film of a photoresist composition comprising a polymer having an acid labile group-substituted carboxyl group and an acid generator, forming a negative tone pattern from the resist film via exposure and organic solvent development, coating the resist pattern with a shrink agent, i.e., a solution of a polymer comprising recurring units capable of forming lactam under the action of acid as represented by formula (1) in an ester solvent of 7 to 16 carbon atoms or ketone solvent of 7 to 16 carbon atoms which does not dissolve the resist pattern, baking, and removing the excessive shrink agent via organic solvent development again. The size of spaces in the resist pattern can be shrunk in a precisely size-controlled manner.

BRIEF DESCRIPTION OF DRAWINGS

FIGS. 1A to 1C illustrate, in cross-sectional view, early steps of a pattern forming or shrinking process according to the invention; FIG. 1A showing a photoresist film formed on a substrate; FIG. 1B showing the photoresist film during exposure; and FIG. 1C showing pattern formation after PEB and development of the photoresist film.

FIGS. 2D to 2F illustrate, in cross-sectional view, later steps of the pattern forming or shrinking process according to the invention; FIG. 2D showing a shrink agent coated on the resist pattern; FIG. 2E showing the resist pattern whose spaces have been shrunk by baking and removal of the excessive shrink agent; and FIG. 2F showing dry etching of the substrate through the shrunk space pattern as a mask.

DESCRIPTION OF PREFERRED EMBODIMENTS

The terms “a” and “an” herein do not denote a limitation of quantity, but rather denote the presence of at least one of the referenced item. “Optional” or “optionally” means that the subsequently described event or circumstances may or may not occur, and that description includes instances where the event or circumstance occurs and instances where it does not. As used herein, the notation (C_(n)-C_(m)) means a group containing from n to m carbon atoms per group. As used herein, the term “film” is used interchangeably with “coating” or “layer.”

The abbreviations and acronyms have the following meaning.

-   -   EB: electron beam     -   Mw: weight average molecular weight     -   Mn: number average molecular weight     -   Mw/Mn: molecular weight distribution or dispersity     -   GPC: gel permeation chromatography     -   PEB: post-exposure bake     -   PAG: photoacid generator     -   LWR: line width roughness     -   LER: line edge roughness

Seeking a shrink material capable of effectively shrinking a resist pattern as developed and a shrink process using the same, the inventors have found the following. A photoresist composition comprising a polymer having an acid labile group-substituted carboxyl group and an acid generator is coated to form a resist film. The resist film is processed via exposure and organic solvent development to form a negative tone resist pattern. Thereafter, the size of spaces in the resist pattern can be shrunk in a precisely size-controlled manner by coating the resist pattern with a shrink agent, i.e., a solution of a polymer comprising recurring units capable of forming lactam under the action of acid as represented by formula (1) in an ester solvent of 7 to 16 carbon atoms or ketone solvent of 7 to 16 carbon atoms, baking, and removing the excessive shrink agent via organic solvent development.

The shrink agent used in the pattern forming process of the invention is a solution of a polymer in a solvent. The polymer is defined as comprising recurring units (a1) capable of forming lactam under the action of acid, represented by the general formula (1).

Herein R¹ is hydrogen or methyl. R² is a straight or branched C₂-C₈ alkylene group. R³ is a straight, branched or cyclic C₁-C₈ alkyl group which may contain an ether moiety, ester moiety or halogen, or an acid labile group. X¹ is phenylene or —C(═O)—O—R⁴— wherein R⁴ is a single bond, a straight, branched or cyclic C₁-C₈ alkylene group, or phenylene group.

Under the action of acid, the recurring unit (a1) of formula (1) forms a lactam ring according to the following scheme.

It should be avoided that when the shrink agent solution is applied onto a resist pattern, the resist pattern is dissolved in the solvent of the shrink agent. To this end, the solvent of the shrink agent must be selected from those solvents that do not dissolve the resist film. The solvents that do not dissolve the resist film include ether solvents of 6 to 12 carbon atoms, alcohol solvents of 4 to 10 carbon atoms, hydrocarbon solvents of 6 to 12 carbon atoms, ester solvents of 7 to 16 carbon atoms, ketone solvents of 7 to 16 carbon atoms, and water. Although a number of water-based shrink agents are already proposed as alluded to previously, they are difficult to quickly apply to large-diameter wafers because of the high surface tension of water. A problem arises particularly in the case of a fine hole pattern formed via negative development. When holes are filled with the shrink agent by spin coating, the water solvent having a high surface tension prevents the shrink agent from burying in the holes to the bottom. In contrast, when a shrink agent dissolved in an organic solvent having a lower surface tension than water is applied, the ability to fill or bury to the hole bottom is improved. Also the organic solvent used in the shrink agent must dissolve the base polymer of the shrink agent. As the solvent capable of dissolving a polymer comprising recurring units having formula (1), ester solvents of 7 to 16 carbon atoms and ketone solvents of 7 to 16 carbon atoms must be selected among the aforementioned organic solvents.

The recurring unit (a1) is derived from a monomer Mal having the following formula.

Herein R¹ to R³, and X¹ are as defined above.

Examples of monomer Mal are shown below. Herein R¹ and R³ are as defined above.

In addition to the recurring units (a1) of formula (1), the polymer for the shrink agent may further comprise recurring units of at least one type selected from recurring units (a3) and (a4) having a substituted carboxyl and hydroxyl group, represented by the general formula (4).

Herein R⁹ and R¹¹ each are hydrogen or methyl. R¹⁰ and R¹³ each are an acid labile group. X² is a single bond, a phenylene or naphthylene group, or —C(═O)—O—R¹⁴—, wherein R¹⁴ is a straight, branched or cyclic C₁-C₁₀ alkylene group which may contain ether, ester, lactone ring or hydroxyl, or a phenylene or naphthylene group. X³ is a single bond, a phenylene or naphthylene group which may contain nitro, cyano or halogen, or —C(═O)—O—R¹⁵—, —C(═O)—NH—R¹⁵—, —O—R¹⁵—, or —S—R¹⁵—, wherein R¹⁵ is a straight, branched or cyclic C₁-C₁₀ alkylene group which may contain ether, ester, lactone ring or hydroxyl, or a phenylene or naphthylene group which may contain a straight, branched or cyclic C₁-C₆ alkyl, alkoxy, acyl, acyloxy, C₂-C₆ alkenyl, alkoxycarbonyl, C₆-C₁₀ aryl, nitro, cyano, or halogen. R¹² is a single bond, a di to penta-valent, straight, branched or cyclic C₁-C₁₆ aliphatic hydrocarbon group, or phenylene group, which may contain an ether or ester moiety. The subscripts a3 and a4 are numbers in the range: 0≦a3<1.0, 0≦a4<1.0, 0≦a3+a4<1.0, preferably 0<a3+a4<1.0, and n is 1 to 4.

In addition to the recurring units (a1) of formula (1), the polymer may further comprise recurring units (a5) and/or (a6) adapted to cyclize to form lactone under the action of acid, represented by the general formula (5).

Herein R¹⁶ and R²² each are hydrogen or methyl. R¹⁷ and R¹⁸ are each independently hydrogen, fluorine, or a straight, branched or cyclic, C₁-C₈ monovalent hydrocarbon group. R¹⁹, R²³ and R²⁵ are each independently hydrogen or a straight, branched or cyclic, C₁-C₂₀ monovalent hydrocarbon group in which any constituent —CH₂— moiety may be replaced by —O— or —C(═O)—, or whose hydrogen may be replaced by halogen. R²⁰ and R²¹ are each independently hydrogen or a straight, branched or cyclic, C₁-C₈ monovalent hydrocarbon group, or R²⁰ and R²¹ may bond together to form a C₃-C₁₇ non-aromatic ring with the carbon atom to which they are attached. R²⁴ is an acid labile group. X⁴ and X⁵ are each independently a straight, branched or cyclic, C₁-C₂₀ divalent hydrocarbon group in which any constituent —CH₂— moiety may be replaced by —O— or —C(═O)—. The subscripts k¹ and k² each are 0 or 1, a5 and a6 are numbers in the range: 0≦a5<1.0, 0≦a6<1.0, and 0≦a5+a6<1.0, preferably 0<a5+a6<1.0.

In addition to the recurring units, the polymer may further comprise recurring units (b) having a hydroxyl, carboxyl, lactone ring, lactam ring, sultone ring, sulfone, sulfonic acid ester, sulfonamide, carboxylic acid amide, nitro, cyano, thienyl, furyl, pyrrole, acid anhydride, imide, —NH—(C═O)—O—, —S—(C═O)—O, or —ON(═O₂)—. Examples of the monomer from which recurring units (b) are derived are shown below.

In the polymer comprising the aforementioned recurring units (a1), (a3), (a4), (a5) and (b), additional recurring units may be copolymerized. Exemplary are recurring units (c) having a non-leaving hydrocarbon group as described in JP-A 2008-281980. Suitable non-leaving hydrocarbon groups include those described in JP-A 2008-281980, and indenes, acenaphthylenes, and norbornadienes. By copolymerizing recurring units (c) having a non-leaving hydrocarbon group, the polymer is improved in solubility in the C₇-C₁₆ ester and C₇-C₁₆ ketone solvents, and also improved in dry etching resistance when the substrate is etched through the pattern after shrinkage.

Further, recurring units (d) having an oxirane or oxetane ring may be copolymerized. Once recurring units (d) having an oxirane or oxetane ring are copolymerized, crosslinking can take place at the interface between the shrink agent and the resist film, leading to an increase of shrinkage. Examples of the monomers from which recurring units (d) having an oxirane or oxetane ring are derived are shown below. Note that R⁴¹ is hydrogen or methyl.

The acid labile group R³ in recurring unit (a1), the acid labile groups R¹⁰ and R¹³ substituting on the carboxyl and hydroxyl groups in formula (4), and the acid labile group R²⁴ in formula (5) in the polymer for the shrink agent, and the acid labile group R⁶ substituting on the carboxyl group in the base polymer for the photoresist (to be described later) may be selected from a variety of such groups while they may be the same or different. Preferred acid labile groups include groups of formula (AL-10), acetal groups of formula (AL-11), tertiary alkyl groups of formula (AL-12), and oxoalkyl groups of 4 to 20 carbon atoms.

In formulae (AL-10) and (AL-11), R⁵¹ and R⁵⁴ each are a monovalent hydrocarbon group, typically a straight, branched or cyclic alkyl group of 1 to 40 carbon atoms, more specifically 1 to 20 carbon atoms, which may contain a heteroatom such as oxygen, sulfur, nitrogen or fluorine. The subscript “a5” is an integer of 0 to 10, preferably 1 to 5. R⁵² and R⁵³ each are hydrogen or a monovalent hydrocarbon group, typically a straight, branched or cyclic C₁-C₂₀ alkyl group, which may contain a heteroatom such as oxygen, sulfur, nitrogen or fluorine. Alternatively, a pair of R⁵² and R⁵³, R⁵² and R⁵⁴, or R⁵³ and R⁵⁴, taken together, may form a ring, specifically aliphatic ring, with the carbon atom or the carbon and oxygen atoms to which they are attached, the ring having 3 to 20 carbon atoms, especially 4 to 16 carbon atoms.

In formula (AL-12), R⁵⁵, R⁵⁶ and R⁵⁷ each are a monovalent hydrocarbon group, typically a straight, branched or cyclic C₁-C₂₀ alkyl group, which may contain a heteroatom such as oxygen, sulfur, nitrogen or fluorine. Alternatively, a pair of R⁵⁵ and R⁵⁶, R⁵⁵ and R⁵⁷, or R⁵⁶ and R⁵⁷, taken together, may form a ring, specifically aliphatic ring, with the carbon atom to which they are attached, the ring having 3 to 20 carbon atoms, especially 4 to 16 carbon atoms.

Illustrative examples of the groups of formula (AL-10) include tert-butoxycarbonyl, tert-butoxycarbonylmethyl, tert-amyloxycarbonyl, tert-amyloxycarbonylmethyl, 1-ethoxyethoxycarbonylmethyl, 2-tetrahydropyranyloxycarbonylmethyl and 2-tetrahydrofuranyloxycarbonylmethyl as well as substituent groups of the following formulae (AL-10)-1 to (AL-10)-10.

In formulae (AL-10)-1 to (AL-10)-10, R⁵⁸ is independently a straight, branched or cyclic C₁-C₈ alkyl group, C₆-C₂₀ aryl group or C₇-C₂₀ aralkyl group; R⁵⁹ is hydrogen or a straight, branched or cyclic C₁-C₂₀ alkyl group; R^(H) is a C₆-C₂₀ aryl group or C₇-C₂₀ aralkyl group; and “a5” is an integer of 0 to 10 as defined above.

Illustrative examples of the acetal group of formula (AL-11) include those of the following formulae (AL-11)-1 to (AL-11)-112.

The polymer may be crosslinked within the molecule or between molecules with acid labile groups of formula (AL-11a) or (AL-11b).

Herein R⁶¹ and R⁶² each are hydrogen or a straight, branched or cyclic C₁-C₈ alkyl group, or R⁶¹ and R⁶², taken together, may form a ring with the carbon atom to which they are attached, and R⁶¹ and R⁶² are straight or branched C₁-C₈ alkylene groups when they form a ring. R⁶³ is a straight, branched or cyclic C₁-C₁₀ alkylene group. Each of b5 and d5 is 0 or an integer of 1 to 10, preferably 0 or an integer of 1 to 5, and c5 is an integer of 1 to 7. “A” is a (c5+1)-valent aliphatic or alicyclic saturated hydrocarbon group, aromatic hydrocarbon group or heterocyclic group having 1 to 50 carbon atoms, which may be separated by a heteroatom such as oxygen, sulfur or nitrogen or in which some of the hydrogen atoms attached to carbon atoms may be substituted by hydroxyl, carboxyl, carbonyl radicals or fluorine atoms. “B” is —CO—O—, —NHCO—O— or —NHCONH—.

Preferably, “A” is selected from divalent to tetravalent, straight, branched or cyclic C₁-C₂₀ alkylene, alkanetriyl and alkanetetrayl groups, and C₆-C₃₀ arylene groups, which may be separated by a heteroatom such as oxygen, sulfur or nitrogen or in which some of the hydrogen atoms attached to carbon atoms may be substituted by hydroxyl, carboxyl, acyl radicals or halogen atoms. The subscript c5 is preferably an integer of 1 to 3.

The crosslinking acetal groups of formulae (AL-11a) and (AL-11b) are exemplified by the following formulae (AL-11)-113 through (AL-11)-120.

Illustrative examples of the tertiary alkyl of formula (AL-12) include tert-butyl, triethylcarbyl, 1-ethylnorbornyl, 1-methylcyclohexyl, 1-ethylcyclopentyl, and tert-amyl groups as well as those of (AL-12)-1 to (AL-12)-16.

Herein R⁶⁴ is independently a straight, branched or cyclic C₁-C₈ alkyl, C₆-C₂₀ aryl or C₇-C₂₀ aralkyl group, or two R⁶⁴ may bond together to form a ring. R⁶⁵ and R⁶⁷ each are hydrogen, methyl or ethyl. R⁶⁶ is a C₆-C₂₀ aryl or C₇-C₂₀ aralkyl group.

Also included are acid labile groups of the formula (AL-12)-17.

Herein R⁶⁴ is as defined above, R⁶⁸ is a single bond or a straight, branched or cyclic C₁-C₂₀ alkylene group or arylene group which may contain a heteroatom such as oxygen, sulfur or nitrogen, and b6 is an integer of 0 to 3. With acid labile groups of formula (AL-12)-17 containing R⁶⁸ representative of a di- or poly-valent alkylene or arylene group, the polymer may be crosslinked within the molecule or between molecules. It is noted that formula (AL-12)-17 is applicable to all the foregoing acid labile groups.

The groups represented by R⁶⁴, R⁶⁵, R⁶⁶ and R⁶⁷ may contain a heteroatom such as oxygen, nitrogen or sulfur. Such groups are exemplified by those of the following formulae (AL-13)-1 to (AL-13)-7.

Of the acid labile groups of formula (AL-12), groups of exo-form structure having the following formula (AL-12)-19 are preferred.

Herein R⁶⁹ is a straight, branched or cyclic C₁-C₈ alkyl group or optionally substituted C₆-C₂₀ aryl group. R⁷⁰ to R⁷⁵, R⁷⁸, and R⁷⁹ are each independently hydrogen or a monovalent C₁-C₁₅ hydrocarbon group, typically alkyl, which may contain a heteroatom, R⁷⁶ and R⁷⁷ are hydrogen; or a pair of R⁷⁰ and R⁷¹, R⁷² and R⁷⁴, R⁷² and R⁷⁵, R⁷³ and R⁷⁵, R⁷³ and R⁷⁹, R⁷⁴ and R⁷⁸, R⁷⁶ and R⁷⁷, or R⁷⁷ and R⁷⁸ may bond together to form a ring, typically aliphatic ring, with the carbon atom to which they are attached, and in this case, the ring-forming participant is a divalent C₁-C₁₅ hydrocarbon group, typically alkylene, which may contain a heteroatom. Also, a pair of R⁷⁰ and R⁷⁹, R⁷⁶ and R⁷⁹, or R⁷² and R⁷⁴ which are attached to vicinal carbon atoms may bond together directly to form a double bond. The formula also represents an enantiomer.

The ester form monomers from which recurring units having an exo-form structure represented by the formula (AL-12)-19 shown below are derived are described in U.S. Pat. No. 6,448,420 (JP-A 2000-327633).

R is hydrogen or methyl. Illustrative non-limiting examples of suitable monomers are given below.

Also included in the acid labile groups of formula (AL-12) are acid labile groups having furandiyl, tetrahydrofurandiyl or oxanorbornanediyl as represented by the following formula (AL-12)-20.

Herein, R⁸⁰ and R⁸¹ are each independently a monovalent hydrocarbon group, typically a straight, branched or cyclic C₁-C₁₀ alkyl group. R⁸⁰ and R⁸¹, taken together, may form an aliphatic hydrocarbon ring of 3 to 20 carbon atoms with the carbon atom to which they are attached. R⁸² is a divalent group selected from furandiyl, tetrahydrofurandiyl and oxanorbornanediyl. R⁸³ is hydrogen or a monovalent hydrocarbon group, typically a straight, branched or cyclic C₁-C₁₀ alkyl group, which may contain a heteroatom.

Recurring units substituted with an acid labile group having furandiyl, tetrahydrofurandiyl or oxanorbornanediyl as represented by the formula:

(wherein R, R⁸⁰ to R⁸³ are as defined above) are derived from monomers, examples of which are shown below. Note that Me is methyl and Ac is acetyl.

Of the acid labile groups of tertiary alkyl form having formula (AL-12), those acid labile groups having a branched alkyl directly attached to the ring offer high solubility in organic solvents. Such acid labile groups are exemplified below. In the following formula, the line segment protruding out of the bracket denotes a valence bond.

In the polymer for the shrink agent, the recurring units (a1), (a3), (a4), (a5), (a6), (b), (c), and (d) are present in proportions a1, a3, a4, a5, a6, b, c, and d, respectively, which satisfy the range: 0<a1≦1.0, 0≦a3≦0.8, 0≦a4≦0.8, 0≦a5≦0.8, 0≦a6≦0.8, 0≦b≦0.9, 0≦c≦0.8, and 0≦d≦0.8;

preferably 0.1≦a1≦0.9, 0≦a3≦0.7, 0≦a4≦0.7, 0≦a5≦0.7, 0≦a6≦0.7, 0.1≦b≦0.9, 0≦c≦0.7, and 0≦d≦0.7; and

more preferably 0.2≦a1≦0.85, 0≦a3≦0.6, 0≦a4≦0.6, 0≦a5≦0.6, 0≦a6≦0.6, 0.2≦b≦0.8, 0≦c≦0.6, and 0≦d≦0.6; provided that a1+a3+a4+a5+a6+b+c+d=1.

On the other hand, the base resin in the resist composition used to form a resist pattern is a polymer comprising recurring units (a2) having an acid labile group-substituted carboxyl group, preferably represented by the general formula (2).

Herein R⁵ is hydrogen or methyl. R⁶ is an acid labile group. Z is a single bond or —C(═O)—O—R⁷— wherein R⁷ is a straight, branched or cyclic C₁-C₁₀ alkylene group which may contain an ether or ester moiety, or naphthylene group, and a2 is a number in the range: 0<a2<1.0.

In the polymer comprising recurring units (a2) for use in the resist composition, recurring units (b) as described above may be copolymerized for improving the insolubility of the exposed region in organic solvent developer, improving adhesion to the substrate, and preventing pattern collapse. Further, there may be copolymerized recurring units having an adhesive group selected from among hydroxyl, lactone ring, ether, ester, carbonyl and cyano groups as described in JP-A 2012-037867, paragraphs [0076]-[0084], an indene, acenaphthylene, chromone, coumarin, and norbornadiene as described in paragraph [0085], a styrene, vinylnaphthalene, vinylanthracene, vinylpyrene, and methyleneindane as described in paragraph [0088], and an acid generator in the form of an onium salt having polymerizable olefin as described in paragraphs [0089]-[0091].

The following discussion applies to both the polymer serving as the shrink agent and the polymer serving as the base resin in the resist composition, both used in the patterning process. The polymer should preferably have a weight average molecular weight (Mw) in the range of 1,000 to 500,000, and more preferably 2,000 to 100,000, as measured by GPC versus polystyrene standards. If Mw is too low, in the case of shrink agent, the amount of shrinkage may become excessive or even uncontrollable due to an extended acid diffusion distance, and in the case of resist composition, the diffusion distance of acid generated by PAG may be extended to invite a drop of resolution. If Mw is too high, in the case of shrink agent, the solubility of the polymer in stripper solvent may be reduced, leaving scum in spaces at the end of removal step, and in the case of resist composition, a footing phenomenon is likely to occur after pattern formation.

If a polymer has a wide molecular weight distribution or dispersity (Mw/Mn), which indicates the presence of lower and higher molecular weight polymer fractions, there is a possibility that foreign matter is left on the pattern or the pattern profile is degraded. The influences of molecular weight and dispersity become stronger as the pattern rule becomes finer. Therefore, the multi-component copolymer should preferably have a narrow dispersity (Mw/Mn) of 1.0 to 2.0, especially 1.0 to 1.5, in order to provide a resist composition suitable for micropatterning to a small feature size.

It is understood that a blend of two or more polymers which differ in compositional ratio, molecular weight or dispersity is acceptable.

The polymers used herein may be synthesized by any desired method, for example, by dissolving one or more monomers in an organic solvent, adding a radical initiator thereto, and effecting heat polymerization. The monomers used herein include monomers corresponding to recurring units (a1), (b) and other units in the case of shrink agent polymer, and monomers corresponding to acid labile group-bearing recurring units (a2), adhesive group-bearing recurring units (b) and the like in the case of resist polymer, and other unsaturated bond-bearing monomers. Examples of the organic solvent which can be used for polymerization include toluene, benzene, tetrahydrofuran, diethyl ether and dioxane. Examples of the polymerization initiator used herein include 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis(2,4-dimethyl-valeronitrile), dimethyl 2,2-azobis(2-methylpropionate), benzoyl peroxide, and lauroyl peroxide. Preferably the system is heated at 50 to 80° C. for polymerization to take place. The reaction time is 2 to 100 hours, preferably 5 to 20 hours. The acid labile group that has been incorporated in the monomer may be kept as such, or the acid labile group may be once removed with an acid catalyst and the resulting polymer be protected or partially protected. In the polymer serving as the shrink agent, recurring units (a1) and (b) may be arranged randomly or blockwise.

The shrink agent used in the pattern forming process further contains an organic solvent and optionally a salt, basic compound and surfactant.

It is essential that the organic solvent do not dissolve the resist film after development. The organic solvent is selected from ester solvents of 7 to 16 carbon atoms and ketone solvents of 7 to 16 carbon atoms. Suitable ester solvents include amyl acetate, isoamyl acetate, 2-methylbutyl acetate, hexyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, hexyl formate, ethyl valerate, propyl valerate, isopropyl valerate, butyl valerate, isobutyl valerate, tert-butyl valerate, amyl valerate, isoamyl valerate, ethyl isovalerate, propyl isovalerate, isopropyl isovalerate, butyl isovalerate, isobutyl isovalerate, tert-butyl isovalerate, isoamyl isovalerate, ethyl 2-methylvalerate, butyl 2-methylvalerate, ethyl pivalate, propyl pivalate, isopropyl pivalate, butyl pivalate, tert-butyl pivalate, ethyl pentenoate, propyl pentenoate, isopropyl pentenoate, butyl pentenoate, tert-butyl pentenoate, propyl crotonate, isopropyl crotonate, butyl crotonate, tert-butyl crotonate, butyl propionate, isobutyl propionate, tert-butyl propionate, benzyl propionate, ethyl hexanoate, allyl hexanoate, propyl butyrate, butyl butyrate, isobutyl butyrate, 3-methylbutyl butyrate, tert-butyl butyrate, ethyl 2-methylbutyrate, isopropyl 2-methylbutyrate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, ethyl phenylacetate, and 2-phenylethyl acetate. Suitable ketone solvents include 2-heptanone, 3-heptanone, 4-heptanone, 2-octanone, 3-octanone, 4-octanone, 2-nonanone, 3-nonanone, 4-nonanone, 5-nonanone, diisobutyl ketone, ethylcyclohexanone, ethylacetophenone, ethyl n-butyl ketone, di-n-butyl ketone, and diisobutyl ketone. These solvents may be used alone or in admixture of two or more.

For the purpose of preventing intermixing of the shrink agent and the resist pattern, any of C₃-C₁₀ alcohol, C₈-C₁₂ ether, C₆-C₁₂ alkane, alkene, alkyne and aromatic solvents may be blended with the above solvent. Specifically, suitable alkanes of 6 to 12 carbon atoms include hexane, heptane, octane, nonane, decane, undecane, dodecane, methylcyclopentane, dimethylcyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, cycloheptane, cyclooctane, and cyclononane. Suitable alkenes of 6 to 12 carbon atoms include hexene, heptene, octene, cyclohexene, methylcyclohexene, dimethylcyclohexene, cycloheptene, and cyclooctene. Suitable alkynes of 6 to 12 carbon atoms include hexyne, heptyne, and octyne. Suitable alcohols of 3 to 10 carbon atoms include n-propyl alcohol, isopropyl alcohol, 1-butyl alcohol, 2-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, tert-amyl alcohol, neopentyl alcohol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-3-pentanol, cyclopentanol, 1-hexanol, 2-hexanol, 3-hexanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-ethyl-1-butanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 4-methyl-3-pentanol, cyclohexanol, and 1-octanol. Suitable ether compounds of 8 to 12 carbon atoms include di-n-butyl ether, diisobutyl ether, di-sec-butyl ether, di-n-pentyl ether, diisopentyl ether, di-sec-pentyl ether, di-tert-amyl ether, and di-n-hexyl ether. Suitable aromatic solvents include toluene, xylene, ethylbenzene, isopropylbenzene, tert-butylbenzene, mesitylene, and anisole. The solvents may be used alone or in admixture.

In the shrink agent solution, the solvent is preferably used in an amount of 100 to 100,000 parts, more preferably 200 to 50,000 parts by weight per 100 parts by weight of the polymer.

To the shrink agent, a salt and basic compound may be added if desired. The salt that can be added is typically selected from sulfonium salts and iodonium salts which are typically added to resist compositions, and ammonium salts. The basic compound that can be added may be selected from those basic compounds which are typically added to resist compositions, for example, primary, secondary and tertiary aliphatic amines, mixed amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having carboxyl group, nitrogen-containing compounds having sulfonyl group, nitrogen-containing compounds having hydroxyl group, nitrogen-containing compounds having hydroxyphenyl group, alcoholic nitrogen-containing compounds, amide derivatives, and imide derivatives. The addition of the salt or basic compound is effective for suppressing excessive diffusion of acid from within the resist film and for controlling the amount of shrinkage. The surfactant that can be added may be selected from those surfactants which are typically added to resist compositions.

As the salt, salt compounds having the general formulae (3)-1 and (3)-2 are preferred. R⁸—CO₂ ⁻M⁺  (3)-1 R⁹—SO₃ ⁻M⁺  (3)-2 Herein R⁸ and R⁹ each are a straight, branched or cyclic C₁-C₂₀ alkyl group, C₂-C₂₀ alkenyl group or C₆-C₂₀ aryl group which may contain fluorine, ether moiety, ester moiety, lactone ring, lactam ring, carbonyl moiety, amino moiety or hydroxyl moiety, and M is sulfonium, iodonium or ammonium.

Examples of the anion: R⁸—CO₂ ⁻ are shown below.

Examples of the anion: R⁹—SO₃ ⁻ are shown below.

Of the salt compounds of formula (3)-1, sulfonium, iodonium and ammonium salts of carboxylic acid represented by formulae (P1a-1) to (P1a-3) are preferred. Of the salt compounds of formula (3)-2, sulfonium, iodonium and ammonium salts of sulfonic acid represented by formulae (P1b-1) to (P1b-3) are preferred. Acid diffusion may be effectively controlled by adding these salts.

Herein R^(101a), R^(101b), R^(101c) and R^(101d) are each independently a straight, branched or cyclic C₁-C₁₂ alkyl, alkenyl, oxoalkyl or oxoalkenyl, C₆-C₂₀ aryl, or C₇-C₁₂ aralkyl or aryloxoalkyl group, in which some or all hydrogen atoms may be replaced by alkoxy or other groups, R^(101b) and R^(101c) may bond together to form a ring which may contain an ether, ester, sultone or amino moiety, each of R^(101b) and R^(101c) is C₁-C₁₀ alkylene or arylene when they form a ring. R⁸ is as defined above.

In the shrink agent, preferably the salt is used in an amount of 0 to 50 parts by weight, the basic compound is used in an amount of 0 to 30 parts by weight, and the surfactant is used in an amount of 0 to 10 parts, more preferably 0 to 5 parts by weight, all per 100 parts by weight of the polymer. When added, each additive is preferably used in an amount of at least 0.1 part by weight.

The resist composition comprises the polymer as base resin, an organic solvent, and an acid generator (i.e., compound capable of generating an acid in response to high-energy radiation), and optionally, a dissolution regulator, basic compound, surfactant, acetylene alcohol, and other components.

Specifically, the resist composition contains an acid generator such that it may function as a chemically amplified resist composition. The acid generator is typically a compound capable of generating an acid in response to actinic light or radiation, known as photoacid generator (PAG). An appropriate amount of the PAG used is 0.5 to 30 parts, more preferably 1 to 20 parts by weight per 100 parts by weight of the base resin. The PAG is any compound capable of generating an acid upon exposure to high-energy radiation. Suitable PAGs include sulfonium salts, iodonium salts, sulfonyldiazomethane, N-sulfonyloxyimide, and oxime-O-sulfonate acid generators. The acid generators may be used alone or in admixture of two or more. Exemplary of the acid generated by PAG are sulfonic acids, imidic acids and methide acids. Of these, sulfonic acids which are fluorinated at α-position are most commonly used. Where the acid labile group is an acetal group susceptible to deprotection, fluorination at α-position is not always necessary. Where the base polymer has recurring units of acid generator copolymerized therein, the acid generator need not be separately added.

Examples of the organic solvent used herein are described in JP-A 2008-111103, paragraphs [0144] to [0145] (U.S. Pat. No. 7,537,880). Specifically, exemplary solvents include ketones such as cyclohexanone and methyl-2-n-amyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; esters such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, and propylene glycol mono-tert-butyl ether acetate; and lactones such as γ-butyrolactone, and mixtures thereof. Where an acid labile group of acetal form is used, a high-boiling alcohol solvent such as diethylene glycol, propylene glycol, glycerol, 1,4-butanediol or 1,3-butanediol may be added for accelerating deprotection reaction of acetal.

Exemplary basic compounds include primary, secondary and tertiary amine compounds, specifically amine compounds having a hydroxyl, ether, ester, lactone, cyano or sulfonate group, as described in JP-A 2008-111103, paragraphs [0146] to [0164], and compounds having a carbamate group, as described in JP 3790649. Also, onium salts such as sulfonium salts, iodonium salts and ammonium salts of sulfonic acids which are not fluorinated at α-position as described in US 2008153030 (JP-A 2008-158339) and similar onium salts of carboxylic acid as described in JP 3991462 and JP 4226807 may be used as the quencher. They may also be added to the shrink agent.

Where the acid labile group is an acetal group which is very sensitive to acid, the acid for eliminating the protective group need not necessarily be a sulfonic acid which is fluorinated at α-position, imidic acid or methide acid. Even with a sulfonic acid which is not fluorinated at α-position, deprotection reaction may take place in some cases. Since an onium salt of sulfonic acid cannot be used as the quencher in this event, an onium salt of imidic acid is preferably used alone.

Exemplary surfactants are described in JP-A 2008-111103, paragraphs [0165]-[0166]. Exemplary dissolution regulators are described in JP-A 2008-122932 (US 2008090172), paragraphs [0155]-[0178], and exemplary acetylene alcohols in paragraphs [0179]-[0182].

Also a polymeric additive may be added for improving the water repellency on surface of a resist film as spin coated. This additive may be used in the topcoatless immersion lithography. These additives have a specific structure with a 1,1,1,3,3,3-hexafluoro-2-propanol residue and are described in JP-A 2007-297590 and JP-A 2008-111103. The water repellency improver to be added to the resist composition should be soluble in the organic solvent as the developer. The water repellency improver of specific structure with a 1,1,1,3,3,3-hexafluoro-2-propanol residue is well soluble in the developer. A polymer having an amino group or amine salt copolymerized as recurring units may serve as the water repellent additive and is effective for preventing evaporation of acid during PEB and avoiding any hole pattern opening failure after development. An appropriate amount of the water repellency improver is 0.1 to 20 parts, preferably 0.5 to 10 parts by weight per 100 parts by weight of the base resin.

Notably, an appropriate amount of the organic solvent is 100 to 10,000 parts, preferably 300 to 8,000 parts by weight, and an appropriate amount of the basic compound is 0.0001 to 30 parts, preferably 0.001 to 20 parts by weight, per 100 parts by weight of the base resin. The dissolution regulator, surfactant and acetylene alcohol may be used in any suitable amounts, depending on their purpose of addition.

Referring to FIGS. 1 and 2, the pattern shrinking process of the invention is described. First, as shown in FIG. 1A, a chemically amplified resist composition is applied onto a processable substrate 20 on a substrate 10 to form a photoresist film 30 thereon. If necessary, a hard mask layer (not shown) may intervene between the resist film 30 and the processable substrate 20. By standard techniques, the resist film 30 is subjected to exposure (FIG. 1B), PEB, and organic solvent development to form a negative resist pattern 30 a (FIG. 1C). A shrink agent 40 is applied onto the negative resist pattern 30 a to cover the pattern as shown in FIG. 2D. The shrink agent coating is baked, during which the heat functions to evaporate off the solvent and to cause the acid to diffuse from the resist pattern 30 into the shrink agent coating 40. With the acid, the polymer in the shrink agent coating undergoes deprotection reaction. Thereafter, a solvent is applied to remove the excessive shrink agent 40, leaving a shrink agent film 40 a over the resist pattern 30 a. This means that the resist pattern 30 a is thickened at 50, that is, the width of spaces in the resist pattern is shrunk as shown in FIG. 2E. Using the shrunk pattern 50 as a mask, the processable substrate 20 is dry etched as shown in FIG. 2F.

The substrate 10 used herein is generally a silicon substrate. The processable substrate (or target film) 20 used herein includes SiO₂, SiN, SiON, SiOC, p-Si, α-Si, TiN, WSi, BPSG, SOG, Cr, CrO, CrON, MoSi, low dielectric film, and etch stopper film. The hard mask may be of SiO₂, SiN, SiON or p-Si. Sometimes, an undercoat in the form of carbon film or a silicon-containing intermediate film may be laid instead of the hard mask, and an organic antireflective coating may be interposed between the hard mask and the resist film.

While a resist film (30) of a chemically amplified resist composition is formed on a processable substrate (20) on a substrate (10) directly or via an intermediate intervening layer as mentioned above, the resist film preferably has a thickness of 10 to 1,000 nm and more preferably 20 to 500 nm. Prior to exposure, the resist film is heated or prebaked, preferably at a temperature of 50 to 180° C., especially 60 to 150° C. for a time of 10 to 300 seconds, especially 15 to 200 seconds.

Next the resist film is exposed to high-energy radiation having a wavelength of up to 400 nm, especially 140 to 250 nm. The high-energy radiation is typically i-line of wavelength 364 nm, KrF excimer laser of wavelength 248 nm, ArF excimer laser of wavelength 193 nm, EUV of wavelength 13.5 nm, or EB. The ArF 193-nm lithography is most preferred. The exposure may be done either in a dry atmosphere such as air or nitrogen stream or by immersion lithography in water. The ArF immersion lithography uses deionized water or liquids having a refractive index of at least 1 and highly transparent to the exposure wavelength such as alkanes as the immersion solvent. In the immersion lithography, the prebaked resist film is exposed to light through a projection lens, with pure water or another liquid introduced between the resist film and the projection lens. Since this allows lenses to be designed to a NA of 1.0 or higher, formation of finer feature size patterns is possible. The immersion lithography is important for the ArF lithography to survive to the 45-nm node. In the case of immersion lithography, deionized water rinsing (or post-soaking) may be carried out after exposure for removing water droplets left on the resist film, or a protective film may be applied onto the resist film after pre-baking for preventing any leach-out from the resist film and improving water slip on the film surface. The resist protective film used in the immersion lithography is preferably formed from a solution of a polymer having 1,1,1,3,3,3-hexafluoro-2-propanol residues which is insoluble in water, but soluble in an alkaline developer liquid, in a solvent selected from alcohols of 4 to 10 carbon atoms, ethers of 8 to 12 carbon atoms, and mixtures thereof. After formation of the photoresist film, deionized water rinsing (or post-soaking) may be carried out for extracting the acid generator and the like from the film surface or washing away particles, or after exposure, rinsing (or post-soaking) may be carried out for removing water droplets left on the resist film.

Exposure is preferably performed in an exposure dose of about 1 to 200 mJ/cm², more preferably about 10 to 100 mJ/cm². This is followed by baking (PEB) on a hot plate at 50 to 150° C. for 1 to 5 minutes, preferably at 60 to 120° C. for 1 to 3 minutes.

Thereafter the exposed resist film is developed with a developer consisting of an organic solvent for 0.1 to 3 minutes, preferably 0.5 to 2 minutes by any conventional techniques such as dip, puddle and spray techniques. In this way, a negative resist pattern is formed on the substrate. The organic solvent used as developer is preferably selected from among 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone, methylcyclohexanone, acetophenone, methylacetophenone, propyl acetate, butyl acetate, isobutyl acetate, amyl acetate, butenyl acetate, isoamyl acetate, propyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl valerate, methyl pentenoate, methyl crotonate, ethyl crotonate, methyl benzoate, ethyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, benzyl propionate, ethyl phenylacetate, and 2-phenylethyl acetate, and mixtures thereof.

At the end of development, the resist film may be rinsed. As the rinsing liquid, a solvent which is miscible with the developer and does not dissolve the resist film is preferred. Suitable solvents include alcohols of 3 to 10 carbon atoms, ether compounds of 8 to 12 carbon atoms, alkanes, alkenes, and alkynes of 6 to 12 carbon atoms, and aromatic solvents. Specifically, suitable alkanes of 6 to 12 carbon atoms include hexane, heptane, octane, nonane, decane, undecane, dodecane, methylcyclopentane, dimethylcyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, cycloheptane, cyclooctane, and cyclononane. Suitable alkenes of 6 to 12 carbon atoms include hexene, heptene, octene, cyclohexene, methylcyclohexene, dimethylcyclohexene, cycloheptene, and cyclooctene. Suitable alkynes of 6 to 12 carbon atoms include hexyne, heptyne, and octyne. Suitable alcohols of 3 to 10 carbon atoms include n-propyl alcohol, isopropyl alcohol, 1-butyl alcohol, 2-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, tert-amyl alcohol, neopentyl alcohol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-3-pentanol, cyclopentanol, 1-hexanol, 2-hexanol, 3-hexanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-ethyl-1-butanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 4-methyl-3-pentanol, cyclohexanol, and 1-octanol. Suitable ether compounds of 8 to 12 carbon atoms include di-n-butyl ether, diisobutyl ether, di-sec-butyl ether, di-n-pentyl ether, diisopentyl ether, di-sec-pentyl ether, di-tert-amyl ether, and di-n-hexyl ether. Suitable aromatic solvents include toluene, xylene, ethylbenzene, isopropylbenzene, tert-butylbenzene, and mesitylene. The solvents may be used alone or in admixture. After the rinse liquid is applied, the substrate may be dried by spin drying and bake. However, rinsing is not essential. As long as the step of spin drying the substrate after the developer is applied thereto is included, the rinsing step may be omitted.

Following the development, the shrink agent of the invention is applied onto the resist pattern to form a shrink agent coating, preferably having a thickness of 1 to 100 nm, more preferably 1.5 to 50 nm. The shrink agent coating is baked at a temperature of 40 to 180° C. for 5 to 300 seconds. Bake functions to evaporate off the solvent and to induce acid diffusion from the resist film to the shrink agent and deprotection reaction to generate carboxyl and/or hydroxyl groups in the shrink agent coating, for thereby rendering the shrink agent coating insoluble in the organic solvent developer due to a polarity change by the generated lactam ring.

Finally, the excessive shrink agent is removed, preferably using the organic solvent developer. This means that development of the resist film and removal of the shrink agent can be performed with an identical organic solvent. The nozzle needed is only one.

EXAMPLE

Examples of the invention are given below by way of illustration and not by way of limitation. The abbreviation “pbw” is parts by weight, and PGMEA is propylene glycol monomethyl ether acetate. For all polymers, Mw and Mn are determined by GPC versus polystyrene standards.

Synthesis Example

Polymers (for use in shrink agent and resist composition) were synthesized by combining suitable monomers in tetrahydrofuran solvent, effecting copolymerization reaction, crystallizing from methanol, repeatedly washing with hexane, isolation and drying. There were obtained random copolymers, designated Polymers 1 to 8, Comparative Polymers 1, 2, Resist Polymer 1, and Water-repellent Polymer 1. The polymers were analyzed for composition by ¹H-NMR spectroscopy and for Mw and Mw/Mn by GPC. The polymers are identified below with their analytical data.

Polymer 1

-   -   Mw=9,900     -   Mw/Mn=1.61

Polymer 2

-   -   Mw=9,800     -   Mw/Mn=1.78

Polymer 3

-   -   Mw=7,900     -   Mw/Mn=1.63

Polymer 4

-   -   Mw=8,200     -   Mw/Mn=1.67

Polymer 5

-   -   Mw=11,900     -   Mw/Mn=1.68

Polymer 6

-   -   Mw=7,700     -   Mw/Mn=1.77

Polymer 7

-   -   Mw=10,500     -   Mw/Mn=1.87

Polymer 8

-   -   Mw=8,500     -   Mw/Mn=1.85

Comparative Polymer 1

-   -   Mw=8,700     -   Mw/Mn=1.73

Comparative Polymer 2

-   -   Mw=8,100     -   Mw/Mn=1.82

Resist Polymer 1

-   -   Mw=7,500     -   Mw/Mn=1.61

Water-Repellent Polymer 1

-   -   Mw=7,800     -   Mw/Mn=1.55

Examples 1 to 22 and Comparative Examples 1 to 4

A shrink agent solution was prepared by mixing the polymer synthesized above (Polymers 1 to 8 or Comparative Polymers 1, 2), additive (e.g., sulfonium salt), and solvent in accordance with the formulation of Tables 1 and 2, and filtering through a Teflon® filter having a pore size of 0.2 μm. Components shown in Tables 1 and 2 are identified below.

Acid Generator: PAG1 of the Following Structural Formula

Sulfonium salts 1 to 10, Iodonium salt 1, Ammonium salts 1, 2 and Amine quenchers 1, 2 of the following structural formulae

TABLE 1 Polymer Additive Organic solvent Shrink agent (pbw) (pbw) (pbw) Shrink agent 1 Polymer 1 — isoamyl acetate (100) (6,000) Shrink agent 2 Polymer 2 Sulfonium salt 1 isoamyl acetate (100) (2.0) (6,000) Shrink agent 3 Polymer 3 Sulfonium salt 1 isoamyl acetate (100) (2.0) (6,000) Shrink agent 4 Polymer 4 Sulfonium salt 1 isoamyl acetate (100) (2.0) (6,000) Shrink agent 5 Polymer 5 Sulfonium salt 1 isoamyl acetate (100) (2.0) (6,000) Shrink agent 6 Polymer 6 Sulfonium salt 1 isoamyl acetate (100) (2.0) (6,000) Shrink agent 7 Polymer 2 Sulfonium salt 2 isoamyl acetate (100) (2.0) (6,000) Shrink agent 8 Polymer 2 Sulfonium salt 3 isoamyl acetate (100) (2.0) (6,000) Shrink agent 9 Polymer 2 Sulfonium salt 4 isoamyl acetate (100) (2.0) (6,000) Shrink agent 10 Polymer 2 Sulfonium salt 5 isoamyl acetate (100) (2.0) (6,000) Shrink agent 11 Polymer 2 Sulfonium salt 6 isoamyl acetate (100) (2.0) (6,000) Shrink agent 12 Polymer 2 Sulfonium salt 7 isoamyl acetate (100) (2.0) (6,000) Shrink agent 13 Polymer 2 Sulfonium salt 8 isoamyl acetate (100) (2.0) (6,000) Shrink agent 14 Polymer 7 Amine quencher 1 isoamyl acetate (100) (0.5) (6,000) Shrink agent 15 Polymer 2 Sulfonium salt 9 isoamyl acetate (100) (2.0)   (600) Shrink agent 16 Polymer 2 Sulfonium salt 10 isoamyl acetate (100) (2.0)   (600) Shrink agent 17 Polymer 2 Iodonium salt 1 ethyl 2-methylvalerate (100) (2.0)   (600) Shrink agent 18 Polymer 2 Ammonium salt 1 2-methylbutyl acetate (100) (2.0)   (600) Shrink agent 19 Polymer 2 Sulfonium salt 1 n-amyl acetate (100) (2.0)   (600) Shrink agent 20 Polymer 2 Sulfonium salt 1 n-hexyl acetate (100) (2.0)   (400) 2-nonane   (200) Shrink agent 21 Polymer 7 Sulfonium salt 1 3-methylbutyl butyrate (100) (2.0)   (500) anisole   (100) Shrink agent 22 Polymer 8 Ammonium salt 2 2-heptanone (100) (2.0)   (500)

TABLE 2 Polymer Additive Organic solvent Shrink agent (pbw) (pbw) (pbw) Comparative Comparative Sulfonium salt 1 isoamyl acetate shrink agent 1 Polymer 1 (2.0)   (600) (100) Comparative Comparative Sulfonium salt 1 isoamyl acetate shrink agent 2 Polymer 2 (2.0)   (600) (100) Comparative Polymer 1 Sulfonium salt 1 PGMEA shrink agent 3 (100) (2.0) (3,000) Comparative Polymer 1 Sulfonium salt 1 butyl acetate shrink agent 4 (100) (2.0) (3,000) Preparation of Resist Composition

A resist composition in solution form was prepared by dissolving a polymer (Resist Polymer 1), acid generator, quencher, and water-repellent polymer in a solvent in accordance with the formulation of Table 3, and filtering through a filter with a pore size of 0.2 μm. The solvent contained 100 ppm of surfactant FC-4430 (3M-Sumitomo Co., Ltd.).

TABLE 3 Acid Water Polymer generator Quencher repellent Organic solvent Resist (pbw) (pbw) (pbw) (pbw) (pbw) Resist 1 Resist PAG1 Amine Water- PGMEA Polymer (10.0) quencher 1 repellent (2,500) 1 (2.0) polymer 1 γ-butyrolactone (100) (3.0)   (200) ArF Lithography Patterning Test

On a silicon wafer, a spin-on carbon film ODL-102 (Shin-Etsu Chemical Co., Ltd.) was deposited to a thickness of 200 nm and a silicon-containing spin-on hard mask SHB-A940 was deposited thereon to a thickness of 35 nm. On this substrate for trilayer process, the resist composition in Table 3 was spin coated, then baked on a hot plate at 100° C. for 60 seconds to form a resist film of 100 nm thick. Using an ArF excimer laser immersion lithography scanner NSR-610C (Nikon Corp., NA 1.30, σ 0.98/0.78, dipole opening 20 deg., azimuthally polarized illumination), the resist film was exposed through a 6% halftone phase shift mask while varying the exposure dose. After the exposure, the resist film was baked (PEB) at 90° C. for 60 seconds and puddle developed in n-butyl acetate for 30 seconds to form a trench pattern having a space width of 45 nm and a pitch of 100 nm.

The shrink agent shown in Tables 1 and 2 was applied onto the resist pattern after development to cover the pattern. The shrink agent coating was baked at the temperature shown in Tables 4 and 5 for 60 seconds. This was followed by puddle development in n-butyl acetate for 20 seconds to remove the excessive shrink agent. Both after development and after shrink treatment, the pattern was observed under a CD-SEM (CG-4000 by Hitachi, Ltd.) to measure the size of trenches at a pitch of 100 nm and edge roughness. The results are shown in Tables 4 and 5.

TABLE 4 Pattern Pattern size after LER after size after LER after Bake removal of removal of development development temp. shrink agent shrink agent Resist (nm) (3σ, nm ) Shrink agent (° C.) (nm) (3σ, nm) Example 1 Resist 1 45 2.7 Shrink agent 1 130 37 2.6 (100) 2 Resist 1 46 2.6 Shrink agent 2 130 39 2.4 (100) 3 Resist 1 45 2.7 Shrink agent 3 125 38 2.2 (100) 4 Resist 1 45 2.7 Shrink agent 4 125 35 2.3 (100) 5 Resist 1 45 2.7 Shrink agent 5 135 37 2.4 (100) 6 Resist 1 45 2.7 Shrink agent 6 135 38 2.2 (100) 7 Resist 1 45 2.7 Shrink agent 7 140 38 2.7 (100) 8 Resist 1 45 2.7 Shrink agent 8 125 39 2.8 (100) 9 Resist 1 45 2.7 Shrink agent 9 135 35 2.4 (100) 10 Resist 1 45 2.5 Shrink agent 10 115 37 2.6 (100) 11 Resist 1 45 2.7 Shrink agent 11 115 35 2.8 (100) 12 Resist 1 45 2.7 Shrink agent 12 115 32 2.6 (100) 13 Resist 1 45 2.7 Shrink agent 13 125 34 2.5 (100) 14 Resist 1 45 2.7 Shrink agent 14 130 36 2.4 (100) 15 Resist 1 45 2.7 Shrink agent 15 130 37 2.5 (100) 16 Resist 1 45 2.7 Shrink agent 16 130 37 2.4 (100) 17 Resist 1 45 2.7 Shrink agent 17 130 38 2.7 (100) 18 Resist 1 45 2.7 Shrink agent 18 130 36 2.4 (100) 19 Resist 1 45 2.7 Shrink agent 19 130 38 2.2 (100) 20 Resist 1 45 2.7 Shrink agent 20 130 39 2.1 (100) 21 Resist 1 45 2.7 Shrink agent 21 135 37 2.6 (100) 22 Resist 1 45 2.7 Shrink agent 22 130 30 2.8 (100)

TABLE 5 Pattern Pattern size after LER after size after LER after Bake removal of removal of development development temp. shrink agent shrink agent Resist (nm) (3σ, nm) Shrink agent (° C.) (nm) (3σ, nm) Comparative 1 Resist 1 45 2.7 Comparative 130 47 3.1 Example (100) shrink agent 1 2 Resist 1 45 2.7 Comparative 130 49 3.1 (100) shrink agent 2 3 Resist 1 45 2.7 Comparative 130 pattern — (100) shrink agent 3 vanished 4 Resist 1 45 2.7 Comparative 130 42 4.5 (100) shrink agent 4

While the invention has been illustrated and described in typical embodiments, it is not intended to be limited to the details shown, since various modifications and substitutions can be made without departing in any way from the spirit of the present invention. As such, further modifications and equivalents of the invention herein disclosed may occur to persons skilled in the art using no more than routine experimentation, and all such modifications and equivalents are believed to be within the spirit and scope of the invention as defined by the following claims.

Japanese Patent Application No. 2014-223972 is incorporated herein by reference.

Although some preferred embodiments have been described, many modifications and variations may be made thereto in light of the above teachings. It is therefore to be understood that the invention may be practiced otherwise than as specifically described without departing from the scope of the appended claims. 

The invention claimed is:
 1. A pattern forming process comprising the steps of: applying a resist composition onto a substrate, said resist composition comprising a polymer comprising recurring units having an acid labile group-substituted carboxyl group, an acid generator and an organic solvent, prebaking to form a resist film, exposing the resist film to high-energy radiation, baking the film, developing the exposed resist film in an organic solvent-based developer to form a negative resist pattern, applying a shrink agent onto the negative resist pattern, said shrink agent being a solution of a polymer comprising recurring units (a1) having the general formula (1) in a solvent selected from the group consisting of ester solvents of 7 to 16 carbon atoms and ketone solvents of 7 to 16 carbon atoms, baking, and removing the excessive shrink agent with the organic solvent-based developer for thereby shrinking the size of spaces in the pattern,

wherein R¹ is hydrogen or methyl, R² is a straight or branched C₂-C₈ alkylene group, R³ is a straight, branched or cyclic C₁-C₈ alkyl group which may contain an ether moiety, ester moiety or halogen, or an acid labile group, X¹ is phenylene or —C(═O)—O—R⁴—, R⁴ is a single bond, a straight, branched or cyclic C₁-C₈ alkylene group, or phenylene group.
 2. The pattern forming process of claim 1 wherein the polymer comprising recurring units (a1) in the shrink agent further comprises recurring units (b) having a hydroxyl, carboxyl, lactone ring, lactam ring, sultone ring, sulfone, sulfonic acid ester, sulfonamide, carboxylic acid amide, nitro, cyano, thienyl, furyl, pyrrole, acid anhydride, imide, —NH—(C═O)—O—, —S—(C═O)—O—, or —ON(═O₂)—.
 3. The pattern forming process of claim 1 wherein the solvent in the shrink agent is at least one solvent selected from the group consisting of ester solvents of 7 to 16 carbon atoms including amyl acetate, isoamyl acetate, 2-methylbutyl acetate, hexyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, hexyl formate, ethyl valerate, propyl valerate, isopropyl valerate, butyl valerate, isobutyl valerate, tert-butyl valerate, amyl valerate, isoamyl valerate, ethyl isovalerate, propyl isovalerate, isopropyl isovalerate, butyl isovalerate, isobutyl isovalerate, tert-butyl isovalerate, isoamyl isovalerate, ethyl 2-methylvalerate, butyl 2-methylvalerate, ethyl pivalate, propyl pivalate, isopropyl pivalate, butyl pivalate, tert-butyl pivalate, ethyl pentenoate, propyl pentenoate, isopropyl pentenoate, butyl pentenoate, tert-butyl pentenoate, propyl crotonate, isopropyl crotonate, butyl crotonate, tert-butyl crotonate, butyl propionate, isobutyl propionate, tert-butyl propionate, benzyl propionate, ethyl hexanoate, allyl hexanoate, propyl butyrate, butyl butyrate, isobutyl butyrate, 3-methylbutyl butyrate, tert-butyl butyrate, ethyl 2-methylbutyrate, isopropyl 2-methylbutyrate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, ethyl phenylacetate, and 2-phenylethyl acetate, and ketone solvents of 7 to 16 carbon atoms including 2-heptanone, 3-heptanone, 4-heptanone, 2-octanone, 3-octanone, 4-octanone, 2-nonanone, 3-nonanone, 4-nonanone, 5-nonanone, diisobutyl ketone, ethylcyclohexanone, ethylacetophenone, ethyl n-butyl ketone, di-n-butyl ketone, and diisobutyl ketone.
 4. The pattern forming process of claim 1 wherein the polymer in the resist composition comprises recurring units (a2) having the general formula (2):

wherein R⁵ is hydrogen or methyl, R⁶ is an acid labile group, Z is a single bond or —C(═O)—O—R⁷—, R⁷ is a straight, branched or cyclic C₁-C₁₀ alkylene group which may contain ether or ester, or naphthylene group, and 0<a2<1.0.
 5. The pattern forming process of claim 1 wherein the developer comprises at least one organic solvent selected from the group consisting of 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone, methylcyclohexanone, acetophenone, methylacetophenone, propyl acetate, butyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate, butenyl acetate, propyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl valerate, methyl pentenoate, methyl crotonate, ethyl crotonate, methyl propionate, ethyl propionate, ethyl 3-ethoxypropionate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, amyl lactate, isoamyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, benzyl propionate, ethyl phenylacetate, and 2-phenylethyl acetate.
 6. The pattern forming process of claim 1 wherein the high-energy radiation in the exposure step is i-line of wavelength 364 nm, KrF excimer laser of wavelength 248 nm, ArF excimer laser of wavelength 193 nm, EUV of wavelength 13.5 nm, or EB.
 7. A shrink agent comprising a polymer and at least one solvent selected from ester solvents of 7 to 16 carbon atoms and ketone solvents of 7 to 16 carbon atoms, said polymer comprising recurring units (a1) having the general formula (1):

wherein R¹ is hydrogen or methyl, R² is a straight or branched C₂-C₈ alkylene group, R³ is a straight, branched or cyclic C₁-C₈ alkyl group which may contain an ether moiety, ester moiety or halogen, or an acid labile group, X¹ is phenylene or —C(═O)—O—R⁴—, R⁴ is a single bond, a straight, branched or cyclic C₁-C₈ alkylene group, or phenylene group.
 8. The shrink agent of claim 7, further comprising at least one of salt compounds having the general formulae (3)-1 and (3)-2: R⁸—CO₂ ⁻M⁺  (3)-1 R⁹—SO₃ ⁻M⁺  (3)-2 wherein R⁸ and R⁹ each are a straight, branched or cyclic C₁-C₂₀ alkyl group, C₂-C₂₀ alkenyl group or C₆-C₂₀ aryl group which may contain fluorine, ether, ester, lactone ring, lactam ring, carbonyl, amino or hydroxyl, and M is sulfonium, iodonium or ammonium. 